Halogen substituted o o dialkyl o cyanophenyl phosphates

ABSTRACT

Halogen-substituted O,O-dialkyl O-cyanophenyl phosphates, i.e. O,O-dialkyl O-cyanophenyl phosphates containing one or two chlorine atoms on one of the alkyl groups and optionally containing a halogen atom on the phenyl ring which possess fungicidal, insecticidal and acaricidal properties.

United States Patent [1 1 Kishino et al.

[451 Sept, 11, 1973 HALOGEN-SUBSTITUTED 0,0-D1ALKYL O-CYANOPHENYLPHOSPHATES inventors: Shigeo Kishino; Yasuo Yamada;

Akio Kudamatsu; Toyohiko Kume, all of Tokyo, Japan Assignee: BayerAktiengesellschaft,

Leverkusen, Germany Int. Cl. C071 9/12, AOln 9/36 Field of Search260/940 References Cited UNITED STATES PATENTS 5/l966 Tamura et al.260/940 Primary Examiner-Lewis Gotts Assistant Examiner--Ant0n H. SuttoAttorneyBurgess, Dinklage & Sprung [5 7] ABSTRACT Halogen-substituted0,0dialkyl O-cyanophenyl phosphates, i.e. 0,0-dialkyl O-cyanophenylphosphates containing one or two chlorine atoms on one of the alkylgroups and optionally containing a halogen atom on the phenyl ring whichpossess fungicidal, insecticidal and acaricidal properties.

16 Claims; No Drawings l HALOGEN-SUBSTITUTED 0,0-DIALKYL O-CYANOPHENYLPHOSPHATES The present invention relates to and has for its objects theprovision of particular new halogensubstituted 0,0-dialkyl O-cyanophenylphosphates, i.e. 0,0-dialkyl O-cyanop'henyl phosphates containing 1 or 2chlorine atoms on one of the alkyl groups and .option- 1 Nos. 13400/63and 279/67 disclose that chloromethyl- O-alkyl-O-cyanophenylphosphonates(or phosphonothionoates) of the formula cicm 0 s ,CN

iso g I 110 Y (I) in which R is an alkyl group, g are insecticides withlow toxicity to warm-blooded ani mals. I i

It has now been found, in accordance with the present invention that theparticular new dialkyl cyanophosphates of the formula i 4 0 0 ON \ll inwhich R stands for'a lower alkyl group,

R stands for lower alkyl group substituted by one or two chlorine atoms,and a X stands for a hydrogen or halogen atom, exhibit strong fungicidaland insecticidal activity, which are not exhibited by known compounds ofanalogous structure.

It has been furthermore found, in accordance with the present invention,that the compounds of formula (III) above may be produced by the processwhich comprises reacting a phosphoric acid diester halide of the formulaP-Hal R 0 (IV) with a phenol or phenolate of the formula I I .oN M0- j iX' (V) in which formulae I g R, R and have the meanings given above, Mstands for ahydrogen atom,ja metal equivalent or an ammonium group, and"Hal stands for a halogen atom,

atom; Surprisingly, the compounds of this invention exhibit excellentbiological'activities of such a broad range that they are effective bothas fungicides and insecticides, and they are of great practical utility.Further, since they are free of harmful heavy metals, they do notpreferably a chlorine cause any problem of such poisons remaining incrops.'

Furthermore, they do not exhibit acute toxicity which is seen inparathion and the like; in fact they have a low toxicity.

They are especially characterized by exccllentfungicidal activity andgrowth-inhibitive activity against fungi and bacteria which infectplants and can be used for controlling diseases caused byvarious fungiof a broad range. Accordingly, they. may be used advantageously asagricultural chemicals. The instant-compounds therefore represent avaluable contribution to the art.

Advantageously, in accordance with the present invention, in the variousformulae herein:

R represents an alkyl of one to four carbon atoms, namely methyl, ethyl,nor isopropyl, or niso-, secor tert-butyl, especially a'straight andbranched chain alkyl group such as methyl, ethyl, and nor iso-propyl,

R represents an alkyl groupof one to-four carbon atoms substituted byone or two chlorine atoms such as chloromethyl 2 -chlor'o-eth'yl,l-chloromethylethyl, l.- ch]oromethyl-Z-chloro-ethyl,i-methyl-S-chloropropyl and l-methyl-Z-chloropropyl, especially or analkali metal such as sodium, potassium or lithium.

The reaction courseis'illustrated by the following reaction scheme:

The starting materials may be used re clearly characterized by formulae(IV) and (V) above, and are well known.

1.- chloromethylethyl, l-chloromethyl-2-chloroe'thyl and As suitablestarting phosphoric acid diester halides of the formula (N) there may bementioned phosphoric acid diester chlorides having an O-methyl-,O-ethyl-, O-n-propylor O-isopropylgroup and an -1- chloromethylethyl-,O-l-chloromethyl-2-chloroethylor O-l-methyl-3-chloropropylgroup, and thelike.

Phenols of the formula (V), include Z-cyanophenol, 4-cyanophenol,2-cyano-4-chlorophenol, 2-cyano-4- bromophenol, 2-chloro-4-cyanophenol,and the like. Salts of these phenols with ammonium or a metal,preferably sodium or potassium, may be also used for the reaction.

The synthesis of the active compounds of the present invention ispreferably carried out in the presence of a solvent or diluent. Anyinert solvent may be used for this purpose. Particularly good results,however, are obtainable with the use of an aliphatic or aromatichydrocarbon (which may be chlorinated) such as methylene chloride; di-,trior tetra-chloroethylene, chloroform, carbon tetrachloride, benzine,benzene, chlorobenzene, toluene or a xylene. Other suitable solventsinclude ethers such as diethyland di-n-butyl-ethers, dioxane andtetrahydrofuran; low molecular weight aliphatic ketones and nitrilessuch as acetone, methylethylketone, methylisopropylketone,methylisobutylketone, acetonitrile and propionitrile; and low boilingaliphatic alcohols such as methanol, ethanol and isopropanol.

The above synthesis of the active compounds of this invention,especially when M is hydrogen, may be performed in the presence of anacid-binder. Any of the compounds which are usually used asacid-binders, for instance, hydroxides, carbonates, bicarbonates andalcoholates of alkali metals, and organic bases (particularly aliphatic,aromatic and heterocyclic amines such as triethylamine, dimethylanilineand pyridine) may be used in the reaction.

When the reaction is effected in the absence of an acid-binder, theintended product of high purity can be obtained in good yield by forminga salt, preferably an ammonium or alkali metal salt, of the appropriatephenol in advance and then reacting the salt with the appropriatephosphoric acid diester halide.

The above-mentioned synthesis may be effectedat a temperature within abroad range. Generally, the reaction is carried out at a temperature offrom -20C. to the boiling point of the reaction mixture. Preferably, thereaction is effected at 0 to 100C. or the boiling point of the mixture,whichever is the lower. It is preferable to carry out the reaction underatmospheric pressure, but it is possible to conduct the reaction underreduced or elevated pressure.

The phosphoric acid esters of this invention have an insect-killingproperty and may be utilized for controlling various harmful insectssuch as sucking insects, biting insects and harmful plant parasites.They are effective as insecticides against insects harmful toagriculture such as insects belonging to the orders Coleoptera,Lepidoptera, Aphidae, Orthoptera, lsoptera, Acarina and Nematodes spidermites and harmful nematodes living in soil. Thus,'they can be used asagents for protecting plants from these insects. The compounds of thisinvention exhibit excellent residual build-up when used as insecticidesagainst sanitarily harmful insects and insects harmful to stored grain,such as flies, aphids, mosquitoes and gnats.

As fungicides, they can be used effectively for eradicating diseases ofplants caused by Archimycetes, Phycomycetes, Ascomycetes,Basidiomycetes, Fungi Imperfecti and other fungi. They are effective inexterminating fungi causing diseases in rice plants, fruit trees andvegetables.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents or extenders of the typeusable in conventional pesticide formulations or compositions, e.g.conventional pesticide dispersible carrier vehicles, such as solutions,emulsions, suspensions, emulsifiable concentrates, spray powders,pastes, soluble powders, dusting agents, granules, etc. These areprepared in known manner, for instance by extending the active compoundswith conventional pesticide dispersible liquid diluent carriers and/ordispersible solid carriers optionally with the use of carrier vehicleassistants, e.g. conventional pesticide surface-active agents, includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case where water is used as diluent, organic solvents may be addedas auxiliary solvents. The following may be chiefly considered for useas conventional carrier vehicles for this purpose: inert dispersibleliquid diluent carriers including inert organic solvents, such asaromatic hydrocarbons (e.g. benzene, toluene, xylene,dimethylnaphthalene, aromatic naphthas, etc.), halogenated, especiallychlorinated, aromatic hydrocarbons (e.g. chlorobenzenes), paraffins(e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g.methylene chloride, carbon tetrachloride, ethylene chloride, etc.),cycloali phatic hydrocarbons (e.g. cyclohexane), alcohols (e.g.methanol, ethanol,-propanol, butanol, etc.), ethers,ether-alcohols (e.g.glycol monomethyl ether, etc.), amines (e.g. ethanol-amine, etc.),amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dim-ethylsulfoxide, etc.),ket0nes (e.g. acetone, methylethylketone,cyclohexanone, etc.), strongly polar solvents such as acetonitrile,and/or water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g., kaolins, alumina,silica, chalk, i.e. calcium" carbonate, talc, kieselguhr,montmorillonite, clay, diatomaceous earth, attapulgite, etc.), andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as. conventional carrier vehicle assistants,e.g. surface-active agents, for

this purpose: emulsifying agents, such as non-ionic and- [or anionicemulsifying agents (e.g..polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, arylsulfonates, etc., and especially alkyl aryl-polyglycol ethers, magnesiumstearate, sodium oleate, etc.); and/or dispersing agents, such aslignin, sulfite waste liquors, methyl cellulose, etc.

As will be appreciated by the artisan, the active compounds according tothe instant invention may be employed alone or in the form ofmixtures'with one another and/or with such solid and/or liquiddispersible carrier vehicles and/or with other known compatible activeagents, especially plant protection agents, such as herbicides,insecticides, acaricides and nematocides,

or fungicides, bactericides, plant growth regulators, an-

vtibiotics, soil disinfectants, including phenoxy compounds,chlorophenol compounds, carbamates, diphenyl ethers, urea compounds,triazine compounds, and other known agricultrual chemicals and/orfertilizers, etc., if desired, or in the form of particular dosagepreparations for specific application made therefrom, such as solutions,emulsions, suspensions, powders, pastes, and graules which are thusready for use. They may also be used as aerosols using as propellantsgaseous diluents or carriers such as freon.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about 0.1 and 95 percent byweight, and preferably 0.5 and 90 percent by weight, of the mixture,whereas carrier composition mixtures suitable for direct application orfield application generally contemplate those in which the activecompound is present in an amount substantially between about 0.0001 20percent, preferably 0.01-5 percent, by weight of the mixture. Thus, thepresent invention contemplates over-all compositions which comprisemixtures of a conventional dispersible carrier vehicle such as (1) adispersible inert finely divided carrier solid, and/or (2) a dispersiblecarrier liquid such as an inert organic solvent and/or water preferablyincluding a surface-active effective amount of a carrier vehicleassistant, e.g. a surface-active agent, such as an emulsifying agentand/or a dispersing agent, and an amount of the active compound which iseffective for the purpose in question and which is generally betweenabout 0.0001-95 percent, and preferably 0.01-95 percent, by weight ofthe mixture.

In particular, the amount of active compound applied per unit areavaries according to the purpose intended, i.e. the effect desired, andthe mode of application. In general, quantities of substantially betweenabout -1000 g of active compound per 10 ares, preferably 40-600 g per 10ares, are applied.

The active compounds can also be used in accordance with the well-knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50-100 microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about '1 quart/acre, preferably 2-16 fluidounces/acre, are sufficient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about to about 95 percent by weight of theactive compound or even the 100 percent active substance alone, e.g.about 20-100 percent by weight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combatting or controlling pests, and more particularlyundesired fungi and insects, which comprise applying to such pests, i.e.at least one of correspondingly (a) such fungi, (b) such insects and (c)the corresponding habitat thereof, i.e. the locus to be protected, apesticidally, i.e. a corresponding fungicidally or insecticidallyeffective or toxic amount of the particular compound of the inventionalone or together with a carrier vehicle as noted above. The instantformulations or compositions are applied in the usual manner, forexample by spraying, atomizing,

scattering, dusting, watering, sprinkling, seed dressing, and the like.

It will be realized, of course, that in connection with the fungicidaland insecticidal use of the instant compounds, the concentration of theparticular active compound utilized in admixture with the carriervehicle will depend upon the intended application and may be variedwithin a fairly wide range depending upon the weather conditions, thelocus to be protected, the purpose for which the active compound isused, e.g. for fungicidal or arthropodicidal or nematocidal effect, andthe plants which are to be controlled or protected. Therefore, inspecial cases, it is possible to go above or below the aforementionedconcentration ranges and amounts per unit area.

The following illustrate, without limitation, examples of formulationswhich may be used in accordance with the present invention:

FORMULATION A 15 parts by weight of compound 3 of Table 5, 80 parts byweight of a mixture of diatomaceous earth and clay (1:5) and 5 parts byweight of an emulsifier (i.e. polyoxyethylene alkylaryl ether) are mixedand crushed to prepare a wettable powder. This formulation may bediluted with water to the desired concentration and then be used as aready-to-use preparation.

. I FORMULATION B 30 parts by weight of compound 4 of Table 5, 30 partsby weight of .xylene, 30 parts by weight of Kawakasol (an aromatichydrocarbon with a boiling range of 150? to 200C.) and l0 parts byweight of the emulsifier Sorpol (i.e. polyoxyethylene alkylaryl ether)are mixed and stirred to prepare an emulsifiable concentrate. Thisformulation may be diluted with water to the desired concentration andthen used as a ready-touse-preparation.

FORMULATION C To a mixture consisting of 10 parts by weight of compound6 of Table 5, 10 parts by weight of bentonite, 78 parts by weight of amixture of talc and clay (1:3) and 2 parts by weight of lignin sulfate,25 parts by weight of water are addedand the mixture is firmly kneaded.

, It is finely cut into granules of'0.5 to 1.5 mm diameter by means of agranulating machine. The granules are then dried at a temperaturebetween 40 to'50C to obtain a granular formulation. This formulationmaydirectly be applied to the soil.

FORMULATION D EXAMPLE 1 TEST A'GAINST RICE BLAST (PIRICULARIA 0RYZAE)/(POT TEST) Preparation of a Sample Composition Solvent: one partby weight of acetone.

Dispersing agent: 0.05 part by weight of sodium oleate.

Other additive: 0.2 part by weight of gelatin.

7 8 Water: 98.75 parts by weight. I i TABLE- 1 g The acme cqmpound, an fSufficlem to 2" Test result against rice blast (Piricularia oryzae) thepredetermined concentration in the ready-to-use preparation, was mixedwith the above amount of the Acme pound component Protective valuePhytosolvent to form a concentrated emulsiflable liquor andconcentration toxicity it was then diluted with the above amount ofwater con- 1 B taining the above amount of the dispersing agent and 50096 55 gelatin to form a sample composition. 2 250 100 Test Procedure 3328 $8 68 I Preventive and curative effect tests: 500 98 62 Rice plants(jukkoku variety) was cultivated in a pot 4 38 :88 3% I of a 12 cmdiameter, and the composition containing 5 250 100 60 the activecompound at the predetermined concentra- 6 2 32 tion was sprayed in anamount of 50 ml per 4 pots. 500 100 77 Half of the chemically sprayedrice plant was kept in 7 :38 g; 52 a chamber maintained at 25C and arelative humidity 8 250 mo 56 I of 100 percent for 2 days from the nextday after the 500 100 7g chemical spraying, and the remaining half waskept in 9 250 500 8 I the same chamber for 2 days from the fourth dayafter 10 250 74 the chemical spraying. While in the said chamber the Hggg 2g rice plant was inoculated twice with a suspension of 5 100 0spores of cultured spores of Piricularia oryzae by spray- 12 65 500 10096 mg. From the results of the infection made the next day 13 250 96 59after the chemical spraying, the protective effect can 500 I00 88 beevaluated, and from the results of the infection 25 14 :38 3g 74 I madethe fourth day after the chemical spraying, the 15 250 94 76 residualeffect can be evaluated. g 3 2 88 Seven days after inoculation, thedegree of infesta- 5 100 g tion was determined by applying a scaleranging from 82 500 100 72 0 to 5, and the protective value of eachparticular ac- "La 250 12 tive compound against Piricularia oryzae wasdeter- (Comparison) S00 46 0 mined in accordance with the formula below.z g

At the same time, the phytotoxicity against rice cially 480 85 42 plantswas determined. avalable product as a comparison) Untreated I Infestedarea of leaf in 3:23; 0 0 Degreeoof mfestanon 0 2 total leaf 1. Thecompound numbers correspond to those in Example 3 and O5 Table 5. i 2.540 2. A means the test result of preventive effect. B means the testresult, 2 5 1() of curative effect. 3 10-20% 3. lll-a denotes0,0-diethyl-O(p-cyanophenyl)phosphate (a com- 4 20-40 pound of theformula (III) and disclosed in the specification of Japa- 5 40 or morenese Patent Publication No. 18398/63.)

4. [BF denotes 0,0-diisopropyl-S-benzylthiophosphate.

EXAMPLE 2 TEST AGAINST VARIOUS KINDS OF Protective value 100 Degree ofinfestation of PLANT PATHOGENIC FUNGI treated plants)/(Degree ofinfestation of non-treated plants) X 100 Test Procedure The symbol inthe following Table 1 means that The active compound of this inventionwas incorpothe chemical did not adversely affect the growth of the ratedin a potato agar culture medium to obtain the derice plant. terminedconcentration of the active compound. Then TABLE a ers .aoaifz s'fvlarous fiifio diiiro FU NGI dammit Xantho- Active Pelllcularia me hasAlternaria Sclerotlnia compound Piricularia sasakll (BacterialCollelotrichum kikuchiana Diaporthe Glomerella cinerea con'oenoryzao(Sheath oryzao leaf legenarlurn (Black oitri cingulata (Brown tratlon(Blast) blight) blight) (Anthranose) spot) (Melanose) (Ripe rot) rot)Compound N o. p.p.m. (rice plants) (rice plants) (rice plants) (melons)(pears) (fruit) (grapes) (peach U ntroated control 5 5 5 5 5 5 5 5NOTES.(1) The compound numbers correspond to those in Example 5 andTable 5. (2) Each value in the table is an average value of those of 4Petri dishes. (3) Degree of illfungai growth: 0=no growth; 1=20% of thenon-treated mycerial area; 2=40% of the non-treated myceriai area; 3=60%or the non-treated myceriai area; 4=80% oi the non-treated myeerialarea; 5=the same growth as the non-treated area.

the medium was put into a Petri dish of 9 cm diameter andsolidified. Themedium was inoculated with the plant pathogenic fungi below, and theywere cultured at 27C for 5 days. Then the conditions of the growth ofthe fungi were examined and the activity of the compound was rated on ascale from (no growth of the fungi) to (the fungi grew in a mannersimilar to the untreated control).

EXAMPLE 3 TEST xcxmsrrns' mnrrno'use l0 FLY (MUSCA DOMESTICA) A sheet offilter paper was spread in a Petri dish of 25 9 cm'diameter and 1 ml ofthe above-mentioned diluted liquor containing the active compound at thedetermined concentration was poured into the dish. ThenlO' mature femaleadult house flies were put into the dish and the dish was kept for 24hours in a thermostat chamber maintained at 28C. The number of the deadinsect was counted and the mortality ratio was calculated. A mortalityratio of 100 percent means that all the insects were killed and amortality ratio of 0 percent means that all the insects survived.

TABLE- 3 Results of tests against the adult house fly Mortality ratio 3)Compound No.

I. The compound numbers correspond to those in Example 5 and Table 5.

2. "La denotes 0,0 -diethyl-O-(p-cyanophenyl)phosphate as described inNote (3) of Table 1.

EXAMPLE 4 Test against mosquito (Culex molestus) larvae:

Test Procedure A Petri dish of 9 cm diameter was charged with 100 ml ofan aqueous dilution of the active compound prepared in the same manneras Example 3, at the determined concentration and 25 of fourth-instarmosquito larvae were put into the dish. The dish was kept in athermostat chamber maintained at 28C for 24 hours. Then the number ofdead larvae was counted and the mortality ratio was calculated. Amortality ratio of 100 percent means that all the larvae were killed anda mortality ratio of 0 percent means that all the larvae survived. TABLE 4 Results of tests against mosquito larvae Active compound Mortalityratio Compound No. concentration 2 10:: gm compound numbers correspondto those in Example 5 and a e i i i The following further examples areset forth to illustrate twithout limitation, the manner of producing theinstant compounds according to the present invention:

' EXAMPEE 5 1 1.9 g of 2-cyanophenol and 10.1 g of triethylamine uid,O-ethyl-O-( l -chloromethylethyl )-O-( 2- cyanophenyl)phosphate of theformula I nHiO O OH I ClCH2QHO H: i o. v (3) The product-wascharacterized by a boiling 5633? or l 60-l62'C./0.l mm Hg and arefractive index n,, of 1.4974.

The following compounds could beobtained in an analogous manner:

TABLE 5 Physical properties (Refractive Formula B.P. CJmnLHg, index)Compound N 0.:

1 CN 168-1649 C./0.6......- (ma 1.5067).

ClCHsCHO wlmii chlitmued Physical properties (Refractive FormulaB1P.C./mm.Hg. index) 2 ON nD 1.5185).

CH30\(' .l) 010111 PO P-O 01 ClCHzCHO P-O- 0N ClCHzCHO C1H5O\(H) /P0--CN GICHaCHO L-O Br 0101110110 s ON 153-114 0./0.25 (59 15142 0,1110 fiClCH1\ /PO /CHO 010111 9 ON 187 0./0.25 (1115 15232). "W

C1I-I5O\C|) C1CH1\ -o -01 /CHO 01011:

10 C=HO\O 182 0/055 1.5153).

/CHO CICH:

z a0\fi) 010H, /P-O -CN /CHO 010m 12 0N 163165C.0.25 n 10 1.5052C;H5O\(|) I D 13 CN 163 C. 0.1 0. 1t 39 1.5107 0,11,0 0' I D L-o- -01CICHaCHzCHO C1H 0\fl) P-O 0N C1CH2CH1$HO CHa v TAB'IIE Lemma Physicalproperties (Refractive Fonnula B.P. C./mm.Hg. index) 15 W61 -.'l::::l::fif w CHBO (mg 5170) \ll /PO CN o cmcmcno Hz is CN 165-168 c./0.25 (nnmssn.

ri-CsH1O 0 /PO CICHICHO CH: 17 N 61 15008).

It will be realized by the artisan that all of the forego- C" O 0 CN ingcompounds contemplated by the present invention 1 possess the desiredfungicidal and insecticidal properties, as well as a comparatively lowtoxicity toward I warm-blooded creatures. 01cm (2 it will be appreciatedthat the instant specification and examples are Set forth by way ofillustration and 5. Ester according to claim 1 wherem such ester IS 0-not limitation, and that various modifications andM1704l'chlommethylethyl)'O'(2' changes may be made without departingfrom the spirit cyanophenynphosphate of the formula and scope of thepresent invention.

What is claimed is: g ON 1. Phosphoric acid esters of the formula KE Q lO WV OICHzCHO Rio 0 H: (a)

I v i Q R 0 X in which R stands for a lower alkyl group,

R stands for a lower alkyl group substituted by one or two chlorineatoms, and I X stands for a hydrogen or halogen atom, one of 3. Esteraccording to claim 1 wherein such ester is 0methyl-O-(l-chloromethylethyl)-O-(2- cyanophenyl)phosphate of theformula ON cmo o cicmcno 4. Ester according to claim 1 wherein suchester is 0- 5 methyl-0-( l-chloromethyl-2-chloroethyl)-0-(2-cyanophenyl) phosphate of the formula chlorophenyl) phosphate of theformula Canto 0 ll CICHQCHO so cyanophenynphosphate of the formula l l(b) 8. Esteraccording to claim 1 wherein such ester is O- ethyl-O-(l-chloroniethylethyl)-O-(2-chloro-4- cyanophenylyphosphate" of theformula 15 V 7 l6 9. Ester according to claim 1 wherein such ester is13. Ester according to claim 1 wherein such ester is ethyl-O-(l-chloromethylethyl)-O-(2-cyano-4- O-ethyl-O-(l-methyl-3-chloropropyl)-O-(2-cyano-4- bromophenyl)phosphate of theformula chlorophenyl) phosphate of the formula CN 5 0,1150 0 CN t o m m;orcmcno CH3 (7) l0 ClCHaCI-IMEHO 10. Ester according to claim 1 whereinsuch ester is o ethyl o (1 chloromethy1 2 chloroethyl) O (2 l4. Esteraccording to claim 1 wherein such ester is cyanophenyl) phosphate of theformula O-ethyl-O-( l-methyl-3-chloropropyl)-O-(2-chloro-4- aneahsrlltimhatr of h formula 15. Ester according to claim 1 wherein such esteris 11. Ester according to claim 1 wherein such ester is o l-o (1- hlo-ometh lethyl) ()-(2- O-ethyl-O-(1-chloromethyl-2-chlor0ethyl)-O-(2-nophenynphosphate of the formula cyano-4-chlorophenyl)phosphate of theformula 7 aH1O 0 ON \il smog 0 010% /POCl clcmcrro /CHO OH; (13 01cm 16.Ester according .to claim 1 wherein such ester isO-isopropyl-O-(1-chloromethylethyl)-O-( 2- l2. Ester according to claim1 wherein such ester is cyangghenynghosghate of the formula O-ethyl-O-(1-methyl-3-chloropropyl)-O-( 2- cyanophenyllghosphate of the formula150-0 1-1 0 0 CN II 2 s v /p 0 /PO oicmcno cicmcmcno CH: (14) UNITEDSTATES PATENT OFFICE CERTIFICATE OF, CORRECTION ,Patent No. 3,758,647Dated September 11'. 1973 Inventor(s) SHIGEO KISHINO ET. AL.

It is certified that error appears in the aboveidentified patent andthat said Letters Patent are hereby corrected as shown below:

Column 5, line 3, correct spelling of "agricultural" Column '10, line49,in the formula -"change "CH" to Column 11, composition 14, cancel"CN" 31: the top '1 of' t he. benzene ring.

Signed and sealed this 23rd day of July 1974.

(SEAL)- Attest: v

McCOYY M. GIBSON, JR. c; MARSHALL DANN I Attesting Officer Commissionerof Patents PO'WSO (0459) Y USCOMM-DC 60376-P69 ".5. GOVERNMENT PRINTINGOFFICE Z 1,, 366"3$

2. Esters according to claim 1 in which R1 stands for alkyl of 1-3 carbon atoms, R2 stands for 1-chloro-methyl-ethyl, 1-chloromethyl-2-chloroethyl or 1-methyl-3-chloropropyl and X stands for a hydrogen, chlorine or bromine atom.
 3. Ester according to claim 1 wherein such ester is O-methyl-O-(1-chloromethylethyl)-O-(2-cyanophenyl)phosphate of the formula
 4. Ester according to claim 1 wherein such ester is O-methyl-O-(1-chloromethyl-2-chloroethyl)-O-(2-cyanophenyl) phosphate of the formula
 5. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethylethyl)-O-(2-cyanophenyl)phosphate of the formula
 6. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethylethyl)-O-(2-cyano-4-chlorophenyl) phosphate of the formula
 7. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethylethyl)-O-(4-cyanophenyl)phosphate of the formula
 8. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethylethyl)-O-(2-chloro-4-cyanophenyl) phosphate of the formula
 9. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethylethyl)-O-(2-cyano-4-bromophenyl)phosphate of the formula
 10. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethyl-2-chloroethyl)-O-(2-cyanophenyl) phosphate of the formula
 11. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-chloromethyl-2-chloroethyl)-O-(2-cyano-4-chlorophenyl)phosphate of the formuLa
 12. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-methyl-3-chloropropyl)-O-(2-cyanophenyl)phosphate of the formula
 13. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-methyl-3-chloropropyl)-O-(2-cyano-4-chlorophenyl) phosphate of the formula
 14. Ester according to claim 1 wherein such ester is O-ethyl-O-(1-methyl-3-chloropropyl)-O-(2-chloro-4-cyanophenyl) phosphate of the formula
 15. Ester according to claim 1 wherein such ester is O-propyl-O-(1-chloromethylethyl)-O-(2-cyanophenyl)phosphate of the formula
 16. Ester according to claim 1 wherein such ester is O-isopropyl-O-(1-chloromethylethyl)-O-(2-cyanophenyl)phosphate of the formula 